Complex of Ruthenium and Osmium, Method of Production Thereof and Use Thereof As (Pre)Catalysts of the Metathesis Reaction

ABSTRACT

Complexes of ruthenium and osmium according to the invention are represented by formula (1), in which M denotes ruthenium or osmium, L denotes a neutral ligand selected from the group comprising amines, imines, phosphines (preferably stilbines, arsines, alcohols, thiols, ethers and thioethers or an N-heterocyclic carbene (NHC) ligand). The compounds of formula (1) occur in the form of two isomers: trans and cis. The method of production of complexes of ruthenium and osmium of formula (1) according to the invention is based on reacting an intermediate of formula (5) with a carbene complex of ruthenium or osmium. The invention also relates to the use of the complexes according to the invention for carrying out metathesis reactions.

The invention relates to novel metal complexes with formula 1, where

-   M denotes ruthenium or osmium,-   L denotes a neutral ligand, selected from the group comprising    amines, imines, phosphines (preferably stilbines, arsines, alcohols,    thiols, ethers and thioethers or the N-heterocyclic carbene ligand    (NHC) represented by formula 9, where    -   B denotes the methylene (—C—), 1,2-ethylene (—C—C—),        1,3-propenyl (—C—C—C—), 1,2-ethenylene (—C═C—) or azaethenyl        (—N═C—) residue, unsubstituted or substituted with halogens,        C₅-C₂₄ aryl, C₁-C₆ alkyl, C₁-C₁₃ perfluoroalkyl, C₁-C₆        cycloalkyl groups, moreover the alkyl groups may be joined        together in a ring; preferably B denotes 1,2-ethylene        (—CH₂—CH₂—)    -   R and R′ denote, independently of one another, C₅-C₂₄ aryl,        C₅-C₂₄ perfluoroaryl, C₁-C₂₆ alkyl, C₁-C₂₆ perfluoroalkyl, C₁-C₇        cycloalkyl groups, unsubstituted or substituted with halogens,        C₅-C₂₄ aryl, C₁-C₆ alkyl, C₁-C₁₃ perfluoroalkyl, C₁-C₆        cycloalkyl groups, moreover the alkyl groups may be joined        together in a ring, preferably R and R′ denote, independently of        one another, phenyl groups substituted with C₁-C₂₆ alkyl        residues, most preferably 2,4,6-trimethylphenyl    -   X and X′ denote an anionic ligand, selected independently of one        another from the group comprising anions of halogens, the        phenolate anion (C₆H₅O⁻) and perfluorophenolate anion (C₆F₅O⁻),        residues of arylcarboxylic, alkylcarboxylic,        perfluoroalkylcarboxylic, alkylsulphonic, arylsulphonic,        perfluoroalkylsulphonic acids, preferably chlorine-   R¹ denotes hydrogen, C₁-C₅ alkyl, C₂-C₅ alkene or C₃-C₇ cycloalkyl,    preferably hydrogen-   R², R³, R⁴, R⁵, R⁶, R⁷ denote, independently, C₁-C₂₅ alkyl, C₁-C₂₅    perfluoroalkyl, C₅-C₂₄ aryl, C₂-C₂₅ alkene or C₃-C₇ cycloalkyl, the    nitro (—NO₂), cyano (—CN), carboxyl (—COOH), ester (—COOR″),    sulphone (—SO₂R″), formyl (—CHO), sulphonamide (—SO₂NR″₂), or ketone    (—COR″) group, in which groups R″ has the following meaning: C₁-C₅    alkyl, C₁-C₅ perfluoroalkyl, C₅-C₂₄ aryl,-   A denotes either nitrogen or carbon placed with an R⁵ group having    the meaning given above    and a method of production thereof.

Compounds of formula 1 occur as two isomers: with formula 1a, in whichatoms X and X′ are arranged trans relative to one another (FIG. 1 a),and with formula 1b, in which atoms X and X′ are arranged cis relativeto one another (FIG. 1 b). The invention also relates to the use of thecompounds of formula 1, both as the pure isomers with formula 1a andwith formula 1b and of mixtures thereof, as (pre)catalysts in processesof metathesis.

In applications of metathesis of olefins in organic synthesis, muchprogress has been achieved in recent years especially in the fields oforganic chemistry and polymer chemistry. Practical applications,especially on an industrial scale, require these complexes to be stablefor a prolonged time in conditions of elevated temperature and it shouldbe possible to store, transport and use them without a protective gasatmosphere. Rapidly initiating (pre)catalysts, for example of formula 2,in which Mes denotes 2,4,6-trimethylphenyl, are often characterized bylower thermal stability. In addition, some metathesis reactions,especially polymerizations (ROMP, ADMET), are difficult to control inthe case of rapidly initiating (pre)catalysts. For this reason it may beadvantageous to use (pre)catalysts that are characterized by a lowerrate of initiation of the metathesis reaction and that possess highthermal and chemical stability (Organometallics 2005, 24, 2255). Thisgroup of (pre)catalysts has found application in particular in polymerchemistry, as initiators permitting controlled polymerization.Representatives of such (pre)catalysts are the pyridine derivativesrepresented by formula 3, in which iPr denotes isopropyl (Journal ofOrganometallic Chemistry 2000, 606, 65) and 4 (Organometallics 2004, 23,5399).

It was found, unexpectedly, that the novel complexes of ruthenium andosmium according to the invention represented by formula 1 areparticularly advantageous as (pre)catalysts, they display a low rate ofinitiation in ring-closure metathesis, and permit a controlled reactionof polymerization by ring opening, while displaying unusually highthermal stability and resistance to oxygen and moisture.

The complexes of ruthenium and osmium according to the invention arerepresented by formula 1, in which:

-   M denotes ruthenium or osmium,-   L denotes a neutral ligand, selected from the group comprising    amines, imines, phosphines (preferably stilbines, arsines, alcohols,    thiols, ethers and thioethers or the N-heterocyclic carbene ligand    (NHC) represented by formula 9, where    -   B denotes the methylene (—C—), 1,2-ethylene (—C—C—),        1,3-propenyl (—C—C—C—), 1,2-ethenylene (—C═C—) or azaethenyl        (—N═C—) residue, unsubstituted or substituted with halogens,        C₅-C₂₄ aryl, C₁-C₆ alkyl, C₁-C₁₃ perfluoroalkyl, C₁-C₆        cycloalkyl groups, moreover the alkyl groups may be joined        together in a ring; preferably B denotes 1,2-ethylene        (—CH₂—CH₂—)    -   R and R′ denote, independently of one another, C₅-C₂₄ aryl,        C₅-C₂₄ perfluoroaryl, C₁-C₂₆ alkyl, C₁-C₂₆ perfluoroalkyl, C₁-C₇        cycloalkyl groups, unsubstituted or substituted with halogens,        C₅-C₂₄ aryl, C₁-C₆ alkyl, C₁-C₁₃ perfluoroalkyl, C₁-C₆        cycloalkyl groups, moreover the alkyl groups may be joined        together in a ring, preferably R and R′ denote, independently of        one another, phenyl groups substituted with C₁-C₂₆ alkyl        residues, most preferably 2,4,6-trimethylphenyl    -   X and X′ denote an anionic ligand, selected independently of one        another from the group comprising anions of halogens, the        phenolate anion (C₆H₅O⁻) and perfluorophenolate anion (C₆F₅O⁻),        residues of arylcarboxylic, alkylcarboxylic,        perfluoroalkylcarboxylic, alkylsulphonic , arylsulphonic,        perfluoroalkylsulphonic acids, preferably chlorine-   R¹ denotes hydrogen, C₁-C₅ alkyl, C₂-C₅ alkene or C₃-C₇ cycloalkyl,    preferably hydrogen-   R², R³, R⁴, R⁵, R⁶, R⁷, denote, independently, C₁-C₂₅ alkyl, C₁-C₂₅    perfluoroalkyl, C₅-C₂₄ aryl, C₂-C₂₅ alkene or C₃-C₇ cycloalkyl, the    nitro (—NO₂), cyano (—CN), carboxyl (—COOH), ester (—COOR″),    sulphone (—SO₂R″), formyl (—CHO), sulphonamide (—SO₂NR″2), or ketone    (—COR″) group, in which groups R″ has the following meaning: C₁-C₅    alkyl, C₁-C₅ perfluoroalkyl, C₅-C₂₄ aryl,-   A denotes either nitrogen or carbon placed with an R⁵ group having    the meaning given above.

The compounds of formula 1 occur as two isomers: 1a, in which atoms Xand X′ are arranged trans relative to one another (FIG. 1 a), and 1b, inwhich atoms X and X′ are arranged cis relative to one another (FIG. 1b).

The method of production of the complexes of ruthenium and osmium offormula 1, in which:

-   M denotes ruthenium or osmium,-   L denotes a neutral ligand, selected from the group comprising    amines, imines, phosphines (preferably stilbines, arsines, alcohols,    thiols, ethers and thioethers or the N-heterocyclic carbene ligand    (NHC) represented by formula 9, where    -   B denotes the methylene (—C—), 1,2-ethylene (—C—C—),        1,3-propenyl (—C—C—C—), 1,2-ethenylene (—C═C—) or azaethenyl        (—N═C—) residue, unsubstituted or substituted with halogens,        C₅-C₂₄ aryl, C₁-C₆ alkyl, C₁-C₁₃ perfluoroalkyl, C₁-C₆        cycloalkyl groups, moreover the alkyl groups may be joined        together in a ring; preferably B denotes 1,2-ethylene        (—CH₂—CH₂—)    -   R and R′ denote, independently of one another, C₅-C₂₄ aryl,        C₅-C₂₄ perfluoroaryl, C₁-C₂₆ alkyl, C₁-C₂₆ perfluoroalkyl, C₁-C₇        cycloalkyl groups, unsubstituted or substituted with halogens,        C₅-C₂₄ aryl, C₁-C₆ alkyl, C₁-C₁₃ perfluoroalkyl, C₁-C₆        cycloalkyl groups, moreover the alkyl groups may be joined        together in a ring, preferably R and R′ denote, independently of        one another, phenyl groups substituted with C₁-C₂₆ alkyl        residues, most preferably 2,4,6-trimethylphenyl    -   X and X′ denote an anionic ligand, selected independently of one        another from the group comprising anions of halogens, the        phenolate anion (C₆H₅O⁻) and perfluorophenolate anion (C₆F₅O⁻),        residues of arylcarboxylic, alkylcarboxylic,        perfluoroalkylcarboxylic, alkylsulphonic, arylsulphonic,        perfluoroalkylsulphonic acids, preferably chlorine-   R¹ denotes hydrogen, C₁-C₅ alkyl, C₂-C₅ alkene or C₃-C₇ cycloalkyl,    preferably hydrogen-   R², R³, R⁴, R⁵, R⁶, R⁷ denote, independently, C₁-C₂₅ alkyl, C₁-C₂₅    perfluoroalkyl, C₅-C₂₄ aryl, C₂-C₂₅ alkene or C₃-C₇ cycloalkyl, the    nitro (—NO₂), cyano (—CN), carboxyl (—COOH), ester (—COOR″),    sulphone (—SO₂R″), formyl (—CHO), sulphonamide (—SO₂NR″2), or ketone    (—COR″) group, in which groups R″ has the following meaning: C₁-C₅    alkyl, C₁-C₅ perfluoroalkyl, C₅-C₂₄ aryl,-   A denotes either nitrogen or carbon placed with an R⁵ group having    the meaning given above,    is based according to the invention on reacting an intermediate with    formula 5, in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and A have the    meanings given above, with a carbene complex of ruthenium or osmium    of formula 6, in which-   M denotes ruthenium or osmium,-   L, L¹ and L² denote, independently of one another, a neutral ligand    selected from the group comprising amines, imines, phosphines,    preferably stilbines, arsines, alcohols, thiols, ethers and    thioethers or an N-heterocyclic carbene ligand (NHC) represented by    formula 9, with L² optionally denoting absence of a ligand    (vacancy),-   R⁸ and R⁹ denote, independently of one another, C₅-C₂₄ aryl groups,    C₁-C₂₆ alkyl groups, C₁-C₇ cycloalkyl groups, unsubstituted or    substituted with halogens, with C₅-C₂₄ aryl groups, with C₁-C₆    alkyl, C₁-C₁₃ perfluoroalkyl and C₁-C₆ cycloalkyl groups, and    optionally groups R⁸ and R⁹ are joined together in a ring or form a    fragment of an aromatic compound, preferably R⁸ denotes hydrogen and    R⁹ denotes phenyl,-   X and X′ have the meaning given above

In the method according to the invention compounds of formula 1a and 1bare obtained as represented in Scheme II (experimental data) in areaction between an N-heterocyclic aromatic compound with formula 5 anda complex of ruthenium or osmium with formula 6, optionally in thepresence of a copper(I) salt, preferably copper(I) chloride. Thereaction is carried out in chlorinated solvents, or in aliphatic,cycloaliphatic and aromatic hydrocarbons, or in mixtures thereof,preferably in methylene chloride far a time from 1 min to 250 h at atemperature from 0 to 150° C.

In addition, the pure isomer with formula lb or a mixture of isomerswith formula 1a and with formula 1b, with proportions of 1a and 1b from100:0 to 0:100, can be obtained as a result of isomerization of asolution of compound 1a in chlorinated solvents, preferably methylenechloride, or in aliphatic, cycloaliphatic and aromatic hydrocarbons, orin mixtures thereof, for a time from 1 minute to 250 h at a temperaturefrom 0 to 150° C.

The synthetic sequences that find general application in the productionof (pre)catalysts with formula 1 are represented generally in Schemes I,III and V and as an example of synthesis of (pre)catalysts of formula10, 11, 12 in Schemes IV and VI-XII and XVII. These routes of synthesisare generally suitable for production of compounds with formula 1.

(Pre)catalysts of formula 1 according to the invention find applicationin a wide range of metathesis reactions. They make it possible toconduct reactions of ring-closure metathesis (RCM), and metathesis ofthe “alkene-alkyne” (ene-yne) type, but they find particular applicationin reactions of ring-opening metathesis polymerization (ROMP).Unexpectedly, the novel (pre)catalysts of formula 1 described hereproved to be slower initiators of RCM reactions than for example thecomparable known (pre)catalyst of formula 3, while retaining goodproperties in the polymerization reaction.

A comparative example using selected (pre)catalysts shows a slowercourse of initiation in the case of compounds of formula 1 (SchemeXIII). Further examples explain the use of the novel (pre)catalysts indifferent types of metathesis reactions: Schemes XIV-XVI.

Examples of application of the invention are presented below.

EXAMPLE I Production of a Compound with Formula 1a Generally (Scheme I)and Particularly of Compound 10a (Scheme II)

Using a protective atmosphere of argon, a Schlenk flask was charged witha solid carbene metal complex of formula 6, in which M denotesruthenium, X and X′ denote chlorine, L denotes absence of a ligand, L¹denotes tricyclohexylphosphine (PCy₃), L² is an NHC ligand with formula9, in which B denotes an ethylene fragment (—CH₂CH₂—), R and R′ denote2,4,5-trimethylphenyl, R⁸ hydrogen and R⁹ phenyl (so-called Grubbssecond-generation catalyst, 102 mg, 0.12 mmol), anhydrous CuCI (13 mg,0.12 mmol), and dry deoxidized CH₂Cl₂ (3 ml) was added. Then a solutionof compound 5 was added, in which R¹═R²═R³═R⁴═R⁵═R⁶═R⁷═H, and A denotescarbon, (20.5 mg, 0.132 mmol) in CH₂Cl₂ (3 ml). The suspension obtainedwas stirred at 40° C. for 20 min. From this moment all subsequentoperations were performed in air, without the need to use the protectiveatmosphere of argon. The reaction mixture was concentrated in anevaporator and the material obtained was fed to a short chromatographycolumn packed with silica gel. The column was developed using pure ethylacetate, collecting a green fraction. After evaporating the solvent andwashing the residue with a small amount of a mixture of ethyl acetateand cold n-pentane, complex 10a was obtained as a green,microcrystalline solid (62 mg, 89% yield). Rf=0.30 (ethyl acetate); ¹ HNMR (500 MHz, CD₂CI₂): 17.05 (s, 1H), 8.36 (dd, 1H, J=1.3, 3.6 Hz),7.26-8.25 (m, 4H), 7.11 (s, 1H), 4.14 (s, 4H), 2.46-2.51 (m, 18H) ppm;¹³C NMR (125 MHz, CD₂CI₂): 288.0, 212.9, 155.7, 151.7, 146.3, 139.0,137.1, 134.0, 1311, 129.7, 129.3, 124.6, 123.4, 116.8, 52.1, 21.3, 19.4ppm; IR (KBr): 3436, 2950, 2915, 2735, 1733, 1607, 1589, 1496, 1481,1417, 1401, 1379, 1318, 1263, 1211, 1175, 1154, 1133, 1095, 1035, 992,915, 850, 833, 792, 773, 748, 646, 618, 592, 578, 512, 426, 414 cm⁻¹; MS(ESI): 625 [M-CI+CH₃CN]⁺. Crystals suitable for X-ray analysis wereobtained from benzene/n-hexane solution.

EXAMPLE II Production of Compound 1b Generally (Scheme III) andParticularly of Compound 10b (Scheme IV)

Using a protective atmosphere of argon, a Schlenk flask was charged witha solid carbene complex of formula 6, in which M denotes ruthenium, Xand X′ denote chlorine, L denotes absence of a ligand, L¹ denotestricyclohexylphosphine (PCy₃), L² is an NHC ligand with formula 9, inwhich B denotes a —CH₂CH₂-fragment, R and R′ denote2,4,5-trimethylphenyl, R⁸ hydrogen and R⁹ phenyl (so-called Grubbssecond-generation catalyst, 102 mg, 0.12 mmol), and dry deoxidizedCH₂Cl₂ (3 ml) was added. Then a solution of compound 5 was added, inwhich R¹═R²═R³═R⁴═R⁵═R⁶═R⁷═H, and A denotes nitrogen, (20.5 mg, 0.132mmol) in CH₂Cl₂ (3 ml). The suspension obtained was stirred at 40° C.for 20 min and was then left unstirred at room temperature for 150 h.From this moment all subsequent operations were performed in air,without the need to use the protective atmosphere of argon. The reactionmixture was concentrated in an evaporator and the material obtained wasfed to a short chromatography column packed with silica gel. The columnwas developed using pure ethyl acetate, collecting a wide greenfraction. After evaporating the solvent and washing the residue with asmall amount of a 1:1 mixture of CH₂Cl₂ and cold n-pentane, compound 10bwas obtained as a dark green, microcrystalline solid (52 mg, 72% yield).IR (KBr): 3447, 2922, 2854, 2735, 1819, 1731, 1628, 1607, 1588, 1570,1496, 1481, 1437, 1400, 1380, 1316, 1291, 1263, 1209, 1176, 1131, 1036,987, 914, 845, 817, 796, 781, 742, 696, 639, 624, 577; 477, 453, 427cm⁻¹. ¹H NMR (500 MHz, CDCl₃) 2.90-1.40 (m, 18H), 4.30-3.60 (m, 4H),6.15-8.05 (m, 4H), 8.14 (d, J=8.1 Hz, 1H), 8.30 (d, J=4.9 Hz, 1H), 17.44(s, 1H) ppm. ¹³C NMR (125 MHz, CDCl₃) 19.1, 21.2, 119.1, 123.5, 124.4,127.6, 130.0, 133.2, 151.2, 152.8, 157.6, 217.7, 282.3 ppm. Crystalssuitable for X-ray analysis were obtained from methylenechloride/n-hexane solution.

EXAMPLE III Production of Compound 1b by Isomerization of 1a Generally(Scheme V) and Particularly of Compound 10b (Scheme VI)

Compound 10a (62 mg, 0.12 mmol) was dissolved in CH₂Cl₂ (1 ml). Thesolution was left in a dark place at room temperature for 3 days, in anargon atmosphere. After this time the solution was concentrated todryness and washed with a mixture of solvents: ethyl acetate/n-pentane,and then methyl chloride/n-pentane. After drying, 10b was obtained as adark green solid (48%, 30 mg). The product possesses analyses that tallywith those obtained previously.

EXAMPLE IV Production of Compound 10 as a Mixture of Isomers 10a and 10b(Scheme XVII)

Using a protective atmosphere of argon, a Schlenk flask was charged witha solid carbene complex of formula 6, in which M denotes ruthenium, Xand X′ denote chlorine, L denotes absence of a ligand, L¹ denotestricyclohexylphosphine (PCy₃), L² is an NHC ligand with formula 9, inwhich B denotes a —CH₂CH₂-fragment, R and R′ denote2,4,5-trimethylphenyl, R⁸ hydrogen and R⁹ phenyl (so-called Grubbssecond-generation catalyst, 102 mg, 0.12 mmol), anhydrous CuCI (13.1 mg,0.132 mmol), and dry deoxidized CH₂Cl₂ (3 ml) was added. Then a solutionof compound 5 was added, in which R¹═R²═R³═R⁴′R⁵═R⁶═R⁷═H, and A denotescarbon, (20.6 mg, 0.132 mmol) in CH₂Cl₂ (3 ml). The suspension obtainedwas stirred at 40° C. for 20 min and was then left unstirred at roomtemperature for 25 h. From this moment all subsequent operations wereperformed in air, without the need to use the protective atmosphere ofargon. The reaction mixture was concentrated in an evaporator and thematerial obtained was fed to a short chromatography column packed withsilica gel. The column was developed using pure ethyl acetate,collecting a wide green fraction. After evaporating the solvent andwashing the residue with a small amount of a 1:1 mixture of CH₂Cl₂ andcold n-pentane, compound 10 was obtained as a mixture of isomers 10a and10b in proportions 50/50, as a dark green, microcrystalline solid (54mg, 72% yield). Rf=0.30 (ethyl acetate).

EXAMPLE V Production of Compound 11a (Scheme VII)

Using a protective atmosphere of argon, a Schlenk flask was charged witha solid carbene complex of formula 6, in which M denotes ruthenium, Xand X′ denote chlorine, L denotes absence of a ligand, L¹ denotestricyclohexylphosphine (PCy₃), L² is an NHC ligand with formula 9, inwhich B denotes a —CH₂CH₂-fragment, R and R′ denote2,4,5-trimethylphenyl, R⁸ hydrogen and R⁹ phenyl (so-called Grubbssecond-generation catalyst, 101.9 mg, 0.12 mmol), anhydrous CuCI (13.1mg, 0.12 mmol), and dry deoxidized CH₂Cl₂ (3 ml) was added. Then asolution of compound 5 was added, in which R¹═R²═R³═R⁴═R⁵═R⁶═R⁷═H, and Adenotes nitrogen, (20.5 mg, 0.132 mmol) in CH₂Cl₂ (3 ml). The suspensionobtained was stirred at 40° C. for 20 min. From this moment allsubsequent operations were performed in air, without the need to use theprotective atmosphere of argon. The reaction mixture was concentrated inan evaporator and the material obtained was fed to a shortchromatography column packed with silica gel. The column was developedusing pure ethyl acetate, collecting a green fraction. After evaporatingthe solvent and washing the residue with a small amount of a mixture ofCH₂Cl₂ and cold n-pentane, complex 11 was obtained as a dark green,microcrystalline solid (52 mg, 72% yield). Rf=0.30 (ethyl acetate); IR(KBr): 3439, 2953, 2920, 2855, 2735, 1943, 1730, 1630, 1607, 1574, 1484,1420, 1379, 1264, 1202, 1149, 1080, 1035, 927, 910, 853, 834, 774, 716,646, 578, 514, 473, 419 cm⁻¹; ¹H NMR (500 MHz, CDCl₃) 2.38-2.50 (m,18H), 4.16 (s, 4H), 7.08 (s, 1H), 7.35-7.62 (s, 1H), 8.38 (m, 1H), 8.45(d, J=2.3 Hz, 1H), 8.57 (d, J=2.2 Hz, 1H), 17.00 (s, 1H) ppm. ¹³C NMR(125 MHz, CDCl₃) 19.2, 21.2, 51.7, 116.6, 124.0, 126.5, 128.6, 129.5,134.9, 136.2, 138.5, 138.8, 141.6, 144.2, 145.6, 147.9, 155.2, 210.5,288.2 ppm. MS (ESI): 626 [M-Cl+CH₃CN]⁺.

EXAMPLE VI Production of Compound 11a (Scheme VIII)

Using a protective atmosphere of argon, a Schlenk flask was charged witha solid carbene complex of formula 6, in which M denotes ruthenium, Xand X′ denote chlorine, L denotes an NHC ligand with formula 9, in whichB denotes a —CH₂CH₂-fragment, R and R′ denote 2,4,5-trimethylphenyl, L1and L2 denote 3-bromopyridine, R⁸ denotes hydrogen and R⁹ phenyl(so-called Grubbs third-generation catalyst, 101.9 mg, 0.12 mmol),anhydrous CuCl (13.1 mg, 0.12 mmol), and dry deoxidized CH₂Cl₂ (3 ml)was added. Then a solution of compound 5 was added, in whichR¹═R²═R³═R⁴═R⁵═R⁶═R⁷═H, and A denotes nitrogen, (20.5 mg, 0.132 mmol) inCH₂Cl₂ (3 ml). The suspension obtained was stirred at 40° C. for 20 min.From this moment all subsequent operations were performed in air,without the need to use the protective atmosphere of argon. The reactionmixture was concentrated in an evaporator and the material obtained wasfed to a short chromatography column packed with silica gel. The columnwas developed using pure ethyl acetate, collecting a green fraction.After evaporating the solvent and washing the residue with a smallamount of a mixture of CH₂Cl₂ and cold n-pentane, complex 11 wasobtained as a dark green, microcrystalline solid (52 mg, 70% yield).

EXAMPLE VII Production of Compound 11b (Scheme IX)

Complex 11a (trans isomer, 55 mg, 0.115 mmol) was dissolved in CH₂Cl₂ (2ml). The solution was left in a dark place at room temperature for 3days, in an argon atmosphere. After this time the solution wasconcentrated to dryness and washed with a mixture of solvents: methylenechloride/n-pentane. After drying, a dark brown solid was obtained (cisisomer, 62%, 34 mg). IR (KBr): 3436, 2921, 2855, 1942, 1725, 1630, 1593,1483, 1442, 1404, 1379, 1314, 1266, 1219, 1195, 1154, 1079, 1034, 929,907, 853, 823, 805, 768, 717, 667, 645, 630, 577, 474, 443, 420 cm¹. ¹HNMR (200 MHz, CDCl₃) 1.84-2.51 (m, 18H), 4.0-4.15 (s, 4H), 7.08 (s, 4H),7.50-7.54 (m, 2H), 7.60-7.58 (m, 1H), 8.38 (m, 1H), 8.48 (d, J=4.2 Hz,1H), 17.30 (s, 1H) ppm.

EXAMPLE VIII Production of Compound 1 Generally (Scheme I) andParticularly of Compound 12a (Scheme X)

Using a protective atmosphere of argon, a Schlenk flask was charged witha solid carbene complex of formula 6, in which M denotes ruthenium, Xand X′ denote chlorine, L denotes absence of a ligand, L¹ and L² denotePCy₃, and R¹⁰ denotes hydrogen and R¹¹ phenyl (so-called Grubbsfirst-generation catalyst, 146.6 mg, 0.25 mmol), anhydrous CuCI (24.6mg, 0.25 mmol), and dry deoxidized CH₂Cl₂ (5 ml) was added. Then asolution of compound 5 was added, in which R¹═R²═R³═R⁴═R⁵═R⁶═R⁷═H, and Adenotes carbon, (34.1 mg, 0.23 mmol) in CH₂Cl₂ (5 ml). The suspensionobtained was stirred at 35° C. for 2 min. From this moment allsubsequent operations were performed in air, without the need to use theprotective atmosphere of argon. The reaction mixture was concentrated inan evaporator and the material obtained was fed to a shortchromatography column packed with silica gel. The column was developedusing pure ethyl acetate, collecting a green fraction. After evaporatingthe solvent and washing the residue with a small amount of a mixture ofCH₂Cl₂ and cold n-pentane, complex 12a was obtained as a pale green,microcrystalline solid (83 mg, 70% yield). Rf=0.40 (ethyl acetate).

EXAMPLE IX Production of Compound 1 Generally (Scheme I) andParticularly of Compound 12a (Scheme XI)

Using a protective atmosphere of argon, a Schlenk flask was charged witha solid carbene complex of formula 6, in which M denotes ruthenium, Xand X′ denote chlorine, L denotes absence of a ligand, L¹ and L² denotePCy₃, and R¹⁰ and R¹¹ denote an indenylidene residue (184.6 mg, 0.20mmol), anhydrous CuCI (21.8 mg, 0.22 mmol), and dry deoxidized CH₂Cl₂ (5ml) was added. Then a solution of compound 5 was added, in whichR¹═R²═R³═R⁴═R⁵═R⁶═R⁷═H, and A denotes carbon, (34.1 mg, 0.22 mmol) inCH₂Cl₂ (5 ml). The suspension obtained was stirred at 35° C. for 2 min.From this moment all subsequent operations were performed in air,without the need to use the protective atmosphere of argon. The reactionmixture was concentrated in an evaporator and the material obtained wasfed to a short chromatography column packed with silica gel. The columnwas developed using pure ethyl acetate, collecting a green fraction.After evaporating the solvent and washing the residue with a smallamount of a mixture of CH₂Cl₂ and cold n-pentane, complex 12a wasobtained as a pale green, microcrystalline solid (84 mg, 70% yield).Rf=0.40 (ethyl acetate).

EXAMPLE X Production of Compound 1 Generally (Scheme I) and Particularlyof Compound 13a (Scheme XII)

Using a protective atmosphere of argon, a Schlenk flask was charged witha solid carbene complex of formula 6, in which M denotes ruthenium, Xand X′ denote chlorine, L denotes absence of a ligand, L¹ denotestricyclohexylphosphine (PCy₃), L² is an NHC ligand with formula 9, inwhich B denotes a —CH₂CH₂-fragment, R and R′ denote2,4,5-trimethylphenyl, R⁸ hydrogen and R⁹ phenyl (so-called Grubbssecond-generation catalyst, 102 mg, 0.12 mmol), anhydrous CuCI (13 mg,0.132 mmol), and dry deoxidized CH₂Cl₂ (3 ml) was added. Then a solutionof compound 5 was added, in which R¹═R³═R⁴═R⁵═R⁶═R⁷═H, R²═CN and Adenotes carbon, (20.5 mg, 0.132 mmol) in CH₂Cl₂ (3 ml). The suspensionobtained was stirred at 40° C. for 20 min. From this moment allsubsequent operations were performed in air, without the need to use theprotective atmosphere of argon. The reaction mixture was concentrated inan evaporator and the material obtained was fed to a shortchromatography column packed with silica gel. The column was developedusing pure ethyl acetate, collecting a green fraction. After evaporatingthe solvent and washing the residue with a small amount of a mixture ofethyl acetate and cold n-pentane, complex 10 was obtained as a green,microcrystalline solid (69 mg, 89% yield). Rf=0.30 (ethyl acetate).

Examples of Applications EXAMPLE XI Use of Compounds 1 as Catalyst inReactions of Ring-Closure Metathesis and ene-yne Cycloisomerization(Schemes XIII-XV)

3-cyclopentene-1,1-diethyl dicarboxylate, P1. A solution of diene S1(84.1 mg, 0.35 mmol) in CH₂Cl₂ (15 ml) was put in a Schlenk flask, and asolution of catalyst 10a (10.8 mg, 0.018 mmol, 5 mol. %) in CH₂Cl₂ (2.5ml) was added at a temperature of 21-23° C. It was stirred at thistemperature, and samples (0.25 ml) of the reaction mixture were takenafter 15 min, 30 min, 45 min, 1 h, 2 h, 4 h, 6 h, 24 h (the reaction wasstopped immediately after taking the sample by adding a suitable amountof 1M ethyl-vinyl ether solution). The degree of conversion in eachsample was calculated on the basis of gas chromatography (32%). ProductP1 was identified by comparing with a reference standard.

In a similar reaction, (pre)catalyst 10b made it possible to obtain P1at a yield of 14%, (pre)catalyst 11a at a yield of 38% and 11b at 18%yield.

In accordance with the data: Organometallics 2004, 23, 5399-5401, thecatalyst of formula 4 catalyses, in similar reaction conditions, theformation of product P1 at a yield of 45%.

EXAMPLE XII

1-[(4-Methylphenyl)sulphonyl]-2,5-dihydro-1H-pyroline, P2. A solution ofcatalyst 11a (10.8 mg, 5 mol. %) in CH₂Cl₂ (2.5 ml) was added to asolution of diene S2 (84.1 mg, 0.35 mmol) in CH₂Cl₂ (15 ml). Thecontents of the flask were stirred at a temperature of 21-23° C. for 24hours. The raw reaction mixture was analysed by gas chromatography. Theyield of product P2 was 56%.

In a similar reaction, (pre)catalyst 10a made it possible to obtain P1at a yield of 41%, (pre)catalyst 10b at a yield of 22% and 11b at 29%yield.

EXAMPLE XII.

2,2-Diphenyl-3-vinyl-2,5-dihydrofuran, P3. A solution of substrate S3(86.9 mg, 0.35 mmol) in CH₂Cl₂ (3.5 ml) was put in a Schlenk flask and asolution of catalyst 10a (2.6 mg, 0.0175 mmol, 5 mol. %) in CH₂Cl₂ (3ml) was added at a temperature of 21-23° C. It was stirred at thistemperature. A sample (0.25 ml) of the reaction mixture was taken after24 h. The degree of conversion in each sample was calculated on thebasis of gas chromatography (95%). Product P1 was identified bycomparing with a reference standard.

In a similar reaction, (pre)catalyst 10b made it possible to obtain P3at a yield of 51%, (pre)catalyst 11a at a yield of 72%.

EXAMPLE XIV. Use of Compound 10a as Catalyst in a Reaction ofRing-Opening Metathesis (Scheme XVI)

Polynorbornene P4. Norbornene (S4, 187 mg, 1.4 mmol) in CH₂Cl₂ (5 ml)was put in a flask and stirred at room temperature. Then a solution ofcatalyst 1 (8.7 mg, 1 mol. %) was added and the contents of the flaskwere stirred at the same temperature for 10 min. The flask contents werepoured into another vessel containing 15 ml of methyl alcohol and awhite solid was precipitated, and was separated by filtration and driedunder reduced pressure using a vacuum pump. Product P4 was obtained (122mg, 92% yield) as a white solid.

1. Complexes of ruthenium or osmium as (pre)catalysts of the metathesisreaction represented by formula 1, in which M denotes ruthenium orosmium, L denotes a neutral ligand, selected from the group comprisingamines, imines, phosphines (preferably), stilbines, arsines, alcohols,thiols, ethers and thioethers or the N-heterocyclic carbene ligand (NBC)represented by formula 9, where B denotes the methylene (—C—),1,2-ethylene (—C—C—), 1,3-propenyl (—C—C—C—), 1,2-ethenylene (—C═C—) orazaethenyl (—N═C—) residue, unsubstituted or substituted with halogens,C₅-C₂₄ aryl, C₁-C₆ alkyl, C₁-C₁₃ perfluoroalkyl, C₁-C₆ cycloalkylgroups, moreover the alkyl groups may be joined together in a ring;preferably B denotes 1,2-ethylene (—CH₂—CH₂—) R and R′ denote,independently of one another, C₅-C₂₄ aryl, C₅-C₂₄ perfluoroaryl, C₁-C₂₆alkyl, C₁-C₂₆ perfluoroalkyl, C₁-C₇ cycloalkyl groups, unsubstituted orsubstituted with halogens, C₅-C₂₄ aryl, C₁-C_(6 alkyl, C) ₁-C₁₃perfluoroalkyl, C₁-C₆ cycloalkyl groups, moreover the alkyl groups maybe joined together in a ring, preferably R and R′ denote, independentlyof one another, phenyl groups substituted with C₁-C₂₆ alkyl residues,most preferably 2,4,6-trimethylphenyl X and X′ denote an anionic ligand,selected independently of one another from the group comprising anionsof halogens, the phenolate anion (C₆H_(S)O⁻) and perfluorophenolateanion (C₆F₅O⁻), residues of arylcarboxylic, alkylcarboxylic,perfluoroalkylcarboxylic, alkylsulphonic, arylsulphonic,perfluoroalkylsulphonic acids, preferably chlorine R¹ denotes hydrogen,C₁-C₅ alkyl, C₂-C₅ alkene or C₃-C₇ cycloalkyl, preferably hydrogen R²,R³, R⁴, R⁵, R⁶, R⁷ denote, independently, C₁-C₂₅ alkyl, C₁-C₂₅perfluoroalkyl, C₅-C₂₄ aryl, C₂-C₂₅ alkene or C₃-C₇ cycloalkyl, thenitro (—NO₂), cyano (—CN), carboxyl (—COOH), ester (—COOR″), sulphone(—SO₂R″), formyl (—CHO), sulphonamide (—SO₂NR″2), or ketone (—COR″)group, in which groups R″ has the following meaning: C₁-C₅ alkyl, C₁-C₅perfluoroalkyl, C₅-C₂₄ aryl, A denotes either nitrogen or carbon placedwith an R⁵ group having the meaning given above.
 2. Complexes accordingto claim 1, characterized in that the compounds with formula 1 have theform of an isomer of formula 1a, in which atoms X and X′ are arrangedtrans relative to one another, as shown in FIG. 1 a and an isomer offormula 1b, in which atoms X and X′ are arranged cis relative to oneanother as shown in FIG. 1 b.
 3. Complexes according to claim 1,characterized in that, in formula 1, A denotes nitrogen or carbon, inligand B denotes a 1,2-ethylene (—C—C—) residue, R and R′ denote aphenyl residue substituted in at least one of the ortho positions,preferably with a mesityl (2,4,5-trimethylphenyl; Mes) residue. 4.Method of production of complexes of ruthenium and osmium of formula 1,in which: M denotes ruthenium or osmium, L denotes a neutral ligand,selected from the group comprising amines, imines, phosphines,preferably stilbines, arsines, alcohols, thiols, ethers and thioethersor the N-heterocyclic carbene ligand (NHC) represented by formula 9,where B denotes the methylene (—C—), 1,2-ethylene (—C—C—), 1,3-propenyl(—C—C—C—), 1,2-ethenylene (—C═C—) or azaethenyl (—N═C—) residue,unsubstituted or substituted with halogens, with C₅-C₂₄ aryl, C₁-C₆alkyl, C₁-C₁₃ perfluoroalkyl, C₁-C₆ cycloalkyl groups, moreover thealkyl groups may be joined together in a ring; preferably B denotes1,2-ethylene (—CH₂—CH₂—) R and R′ denote, independently of one another,C₅-C₂₄ aryl, C₅-C₂₄ perfluoroaryl, C₁-C₂₆ alkyl, C₁-C₂₆ perfluoroalkyl,C₁-C₇ cycloalkyl groups, unsubstituted or substituted with halogens,C₅-C₂₄ aryl, C₁-C₆ alkyl, C₁-C₁₃ perfluoroalkyl, C₁-C₆ cycloalkylgroups, moreover the alkyl groups may be joined together in a ring,preferably R and R′ denote, independently of one another, phenyl groupssubstituted with C₁-C₂₆ alkyl residues, most preferably2,4,6-trimethylphenyl X and X′ denote an anionic ligand, selectedindependently of one another from the group comprising anions ofhalogens, the phenolate anion (C₆H₅O⁻) and perfluorophenolate anion(C₆F₅O⁻), residues of arylcarboxylic, alkylcarboxylic,perfluoroalkylcarboxylic, alkylsulphonic, arylsulphonic,perfluoroalkylsulphonic acids, preferably chlorine R¹ denotes hydrogen,C₁-C₅ alkyl, C₂-C₅ alkene or C₃-C₇ cycloalkyl, preferably hydrogen R²,R³, R⁴, R⁵, R⁶, R⁷ denote, independently, C₁-C₂₅ alkyl, C₁-C₂₅perfluoroalkyl, C₅-C₂₄ aryl, C₂-C₂₅ alkene or C₃-C₇ cycloalkyl, thenitro (—NO₂), cyano (—CN), carboxyl (—COOH), ester (—COOR″), sulphone(—SO₂R″), formyl (—CHO), sulphonamide (—SO₂NR″2), or ketone (—COR″)group, in which groups R″ has the following meaning: C₁-C₅ alkyl, C₁-C₅perfluoroalkyl, C₅-C₂₄ aryl, A denotes either nitrogen or carbon placedwith an R⁵ group having the meaning given above, characterized in thatan intermediate of formula 5, in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and Ahave the meaning given above, is reacted with a carbene complex ofruthenium or osmium of formula 6, in which: M denotes ruthenium orosmium, L, L¹ and L² denote, independently of one another, a neutralligand selected from the group comprising amines, imines, phosphines,preferably stilbines, arsines, alcohols, thiols, ethers and thioethersor an N-heterocyclic carbene ligand (NEC) represented by formula 9, withL² optionally denoting hydrogen—absence of a ligand (vacancy), R⁸ and R⁹denote, independently of one another, C₅-C₂₄ aryl groups, C₁-C₂₆ alkylgroups, C₁-C₇ cycloalkyl groups, unsubstituted or substituted withhalogens, with C₅-C₂₄ aryl groups, with C₁-C₆ alkyl, C₁-C₁₃perfluoroalkyl and C₁-C₆ cycloalkyl groups, and optionally groups R⁸ andR⁹ are joined together in a ring or form a fragment of an aromaticcompound, preferably R⁸ denotes hydrogen and R⁹ denotes phenyl, X and X′have the meaning given above
 5. Method according to claim 4,characterized in that compounds of formula 1a and 1b are obtained asshown in Scheme II, in a reaction between an N-heterocyclic aromaticcompound of formula 5 and a complex of ruthenium or osmium of formula 6,optionally in the presence of a copper(I) salt, preferably copper(I)chloride.
 6. Method according to claim 4, characterized in that thereaction is carried out in chlorinated solvents, or in aliphatic,cycloaliphatic and aromatic hydrocarbons, or in mixtures thereof,preferably in methylene chloride for a time from 1 min to 250 h at atemperature from 0 to 150° C.
 7. Method according to claim 4,characterized in that a pure isomer of formula 1b or a mixture ofisomers of formula 1a and of formula 1b, with ratio of 1a to 1b from100:0 to 0:100, is obtained as a result of isomerization of a solutionof compound 1a in chlorinated solvents, preferably methylene chloride,or in aliphatic, cycloaliphatic and aromatic hydrocarbons, or inmixtures thereof for a time from 1 minute to 250 h at a temperature from0 to 150° C.
 8. Method according to claim 4, characterized in that thesequences of synthesis for production of complexes of formula 1 areshown in Schemes I, III and V, and for synthesis of complexes of formula10, 11, 12 in Schemes II, IV and VI-XII.
 9. Use of complexes of formula1, in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and A have the meaning givenabove, characterized in that they are used as (pre)catalysts in ametathesis reaction.
 10. Use according to claim 9, characterized in thatcompounds of formula 1 are used as (pre)catalysts of ring-closuremetathesis, of cross metathesis and of metathesis of the “alkene-alkyne”(ene-yne) type.
 11. Use according to claim 9, characterized in thatcompounds of formula 1 are used in polymerization processes.